(E)-methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)acrylate → methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)propanoate

HRID 75745Notes

Reaction equation

HRID 75745 reaction equation
[CH2:1]([C@H:8]1[CH2:16][O:15][CH2:14][C@H:13]([NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:12](=[O:25])[O:11][C@@H:10]([CH3:26])[C@@H:9]1[O:27]/[CH:28]=[CH:29]/[C:30]([O:32][CH3:33])=[O:31])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>CCOC(C)=O.[Pd]>[CH2:1]([C@H:8]1[CH2:16][O:15][CH2:14][C@H:13]([NH:17][C:18]([O:20][C:21]([CH3:22])([CH3:23])[CH3:24])=[O:19])[C:12](=[O:25])[O:11][C@@H:10]([CH3:26])[C@@H:9]1[O:27][CH2:28][CH2:29][C:30]([O:32][CH3:33])=[O:31])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 86701238(E)-methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)acrylate

Product 1

HCID 86701237methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)propanoateYield 97%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (E)-methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)acrylate (168 mg, 0.362 mmol, 1.00 equiv) in EtOAc (3.6 mL, 0.1 M) was added 10% Pd/C (19 mg, 0.018 mmol, 0.050 equiv). The flask was equipped with a rubber septum and the atmosphere was replaced with H2 via needle-equipped balloon. After 17 h at room temperature, the catalyst was removed by filtration through Celite® and the pad was flushed with EtOAc. The filtrate was concentrated to provide methyl 3-((3S,6S,7R,8S)-8-benzyl-3-(tert-butoxycarbonylamino)-6-methyl-4-oxo-1,5-dioxonan-7-yloxy)propanoate (163 mg, 97%) as a clear, colorless film: IR (neat film) 3357, 3026, 2978, 2880, 1741, 1711, 1497, 1367, 1294, 1198, 1163, 1070, 1023, 911, 731 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.34-7.27 (m, 2H), 7.24-7.10 (m, 3H), 5.18-5.03 (d, J=8.3 Hz, 1H), 5.01-4.81 (dq, J=9.2, 6.4 Hz, 1H), 4.69-4.47 (q, J=7.3 Hz, 1H), 4.07-3.76 (m, 3H), 3.75-3.61 (s, 3H), 3.53-3.31 (m, 2H), 3.31-3.03 (m, 3H), 2.71-2.52 (t, J=6.2 Hz, 2H), 2.41-2.22 (t, J=12.6 Hz, 1H), 1.98-1.75 (s, 1H), 1.53-1.46 (d, J=6.4 Hz, 3H), 1.46-1.36 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 172.23, 171.73, 139.78, 129.15, 128.44, 126.14, 85.23, 80.11, 75.32, 72.86, 72.28, 67.67, 52.91, 51.82, 47.16, 35.24, 35.05, 28.26, 18.68; HRMS-ESI (m/z) [M+Na]+ calc'd for C24H35NO8Na, 488.2255. found, 488.2260.

Workup

  1. customThe flask was equipped with a rubber septum
  2. customvia needle-equipped balloon
  3. customthe catalyst was removed by filtration through Celite®
  4. customthe pad was flushed with EtOAc
  5. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-f0ea77529b004a2f8183a6a8e33634b9
Source dataset
uspto-grants-2014_09
Patent number
US08835462B2

Reaction notes

Loading…